Olefinic Ester Compositions and Their Use in Oil- and Gas-Related Applications

ABSTRACT

Compositions for treating high-molecular-weight components of a petroleum fluid are generally disclosed. In some embodiments, such compositions include olefinic ester compounds, such as alkyl esters of C 10-18  unsaturated fatty acids. In some embodiments, such compositions are added to a petroleum fluid to improve the rheological properties, e.g., breaking up or inhibiting the precipitation of high-molecular-weight components of petroleum fluids. In some other embodiments, such compositions are used for removing deposits of such high-molecular-weight components from the surfaces of equipment used for extracting or transporting petroleum or natural gas.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit of priority of United StatesProvisional Application Nos.: 61/928,290, filed Jan. 16, 2014;62/006,655, filed Jun. 2, 2014; 62/075,055, filed Nov. 4, 2014;62/081,933, filed Nov. 19, 2014; and 62/089,665, filed Dec. 9, 2014.Each of the foregoing applications is hereby incorporated by referenceas though fully set forth herein in its entirety.

TECHNICAL FIELD

Compositions for treating high-molecular-weight components of apetroleum fluid are generally disclosed. In some embodiments, suchcompositions include olefinic ester compounds, such as alkyl esters ofC₁₀₋₁₈ unsaturated fatty acids. In some embodiments, such compositionsare added to a petroleum fluid to improve the rheological properties,e.g., breaking up or inhibiting the precipitation ofhigh-molecular-weight components of petroleum fluids, such as waxes,asphaltenes, and the like. In some other embodiments, such compositionsare used for removing deposits of such high-molecular-weight componentsfrom the surfaces of equipment used for extracting or transportingpetroleum or natural gas. In some embodiments, the olefinic estercompounds are derived from a natural oil or a natural oil derivative,for example, by catalytic olefin metathesis.

BACKGROUND

Extracted carbonaceous fluids, such as petroleum fluids or natural gas,can contain a variety of high-molecular-weight components thatprecipitate out of the extracted fluid or that deposit onto theequipment used to extract and transport such fluids (e.g., pipelines,tanks, downhole pipes and tubes, and above-ground extraction equipment,such as rigs). The precipitation and deposition of these materials cancause significant problems in extracting these fluids and transportingthem away from the extraction site for refinement.

Petroleum waxes are one class of high-molecular-weight components thatare typically present in extracted carbonaceous fluids (e.g., petroleumfluids), and which can cause the problems described above. Two differentkinds of wax formations are common: paraffin waxes and microcrystallinewaxes. Paraffin waxes are macrocrystalline waxes that tend toprecipitate out as large, flat plates. They are made up primarily ofstraight-chain alkanes having at least 18 carbon atoms up to 75 or morecarbon atoms. In most instances, these waxes have molecular weights thatrange from about 300 to 1200 amu, and more typically from about 300 to600 amu. In contrast, microcrystalline waxes tend to precipitate out asneedle-like structures, and are made up primarily of branched-chainand/or cyclic alkanes. In most instances, such microcrystalline waxeshave molecular weights that range from about 300 up to 2500 amu. Theamount of various wax-forming components in an extracted fluid will varyfrom well to well.

At elevated temperatures, these waxes tend to remain dissolved in theextracted fluid. But as the temperature of the fluid drops, nucleationoccurs and wax deposits develop and grow. The wax appearance temperature(WAT) for a given extracted fluid is the temperature at which the waxmolecules begin to cluster. Therefore, it is desirable to have a lowerWAT, so as to avoid the development of waxy deposits.

Asphaltenes are another class of high-molecular-weight components thatare typically present in extracted carbonaceous fluids (e.g., petroleumfluids), and which can cause the problems described above. Asphaltenesare high-molecular-weight aromatic agglomerates that are generallysoluble in light aromatics (e.g., benzene, toluene, etc.), but which aregenerally insoluble in light paraffins (e.g., n-pentane, n-heptane,etc.). Asphaltenes generally desorb from the extracted fluid as thepressure on the fluid drops, such as when the fluid moves through thedownhole tubing, through pipelines, etc.

Petroleum waxes and asphaltenes may be soluble in certain organicsolvents. However, in many instances, such solvents have a high volatileorganic content (VOC), and thereby may contribute to greenhouse gasproduction and ozone depletion. In some instances, traditional high-VOCsolvents can also be carcinogenic, teratogenic, toxic, or mutagenic.Therefore, a number of common solvents have come under increasedregulatory scrutiny and therefore suffer from decreased use. Suchsolvents include aromatics (e.g., benzene, toluene, xylenes, and thelike), ketones (e.g., methyl ethyl ketone, methyl isobutyl ketone, andthe like), halogenated organics (e.g., dichloromethane,perchloroethylene, and the like), glycol ethers, and alcohols (e.g.,methanol, isopropanol, ethylene glycol, and the like). Therefore, it isgenerally undesirable these days to employ such solvents to addressproblems associated with petroleum waxes and asphaltenes.

Certain derivatives of renewable feedstocks can provide more suitablealternatives to high-VOC solvents. For example, fatty acid alkyl esters(e.g., from the transesterification of vegetable oils, animal fats, orother lipids) can provide environmentally friendly alternatives totraditional oxygenated solvents. Methyl soyate, for example, has a lowVOC value, a high flash point, a low toxicity, and a highbiodegradability. Terpene oils from citrus and pine (d-limonene andpinene, respectively) may also serve as suitable alternatives to certaintraditional organic solvents. Such renewable solvents are not withouttheir problems, however. For example, d-limonene and dipentene (aracemate of d-limonene) are both acute and chronic aquatic toxins, andalso have an irritating and sensitizing effect on the skin. Further,d-limonene is highly inflammable (e.g., more so than petroleumdistillates) and can be subject to fluctuations in supply and price.Fatty acid alkyl esters can overcome some of these deficiencies ofterpene oils, but can also exhibit poor solvency relative to certainincumbents.

In some cases, specialized polymers have been developed to help dispersepetroleum waxes in extracted fluids, thereby inhibiting their ability toagglomerate and have a negative effect on the flow properties of thefluid and accumulate as deposits onto various equipment. But thesepolymers can have the effect of increasing the viscosity of the fluid.So, while use of these polymers may solve certain problems associatedwith wax formation, they create other issues.

Thus, there is a continuing need to develop solvent compounds andcompositions that are renewably sourced, exhibit high solvency towardpetroleum waxes and asphaltenes, and have a desirable health and safetyprofile.

SUMMARY

In a first aspect, the disclosure provides compositions that includeolefinic ester compounds, wherein the olefinic ester compounds areesters of C₁₀₋₁₈ carboxylic acids having one or more carbon-carbondouble bonds. In some embodiments, the esters are C₁₋₆ alkanol esters,such methyl esters, ethyl esters, isopropyl esters, and the like.Further, in some embodiments, the C₁₀₋₁₈ carboxylic acids are C₁₀₋₁₂carboxylic acids having one to three carbon-carbon double bonds. In someembodiments, the compositions consist essentially of or consist of saidolefinic ester compounds. In some embodiments, the compositions includeone or more surfactants, such as non-ionic surfactants. In someembodiments, the surfactants have a hydrophilic-lipophilic balance (HLB)ranging from 4 to 10, or from 5 to 9, and a molecular weight rangingfrom 200 to 800 amu, or from 300 to 600 amu.

In a second aspect, the compositions of the first aspect are cleaningcompositions, such as compositions suitable for use in cleaning gas- oroil-extraction equipment, such as cleaning certain materials or depositsfrom rigs, tuning, pipes, valves, and the like. In some embodiments, thematerials to be removed include asphaltenes and/or petroleum waxes(e.g., macrocrystalline waxes and/or microcrystalline waxes). In somesuch embodiments, the compositions include a surfactant, such as anon-ionic surfactant.

In a third aspect, the compositions of the first aspect are petroleumadditive compositions. In some such embodiments, the compositions areadded to an extracted fluid (e.g., crude oil) to inhibit or prevent theformation and/or precipitation of deposits that include petroleum waxesand/or asphaltenes. In some such embodiments, the compositions include asurfactant, such as a non-ionic surfactant.

In a fourth aspect, the disclosure provides a petroleum composition,including: a petroleum fluid; and a petroleum additive composition ofthe third aspect. In some embodiments, the petroleum additivecomposition makes up no more than 5 percent by weight of the petroleumcomposition, based on the total weight of the composition.

In a fifth aspect, the disclosure provides methods for cleaning asurface, including: providing a surface having a material (e.g., adeposit) disposed thereon, the material including asphaltenes, petroleumwaxes, or a combination thereof; and contacting the material with thecomposition of any of the foregoing aspects. In some embodiments, thesurface is a surface of a component of an oil rig, such as the interiorwall of a pipe, tube, or tank, or a gauge, valve, pressure regulator,and the like.

In a sixth aspect, the disclosure provides methods of reducingagglomerates in a petroleum fluid, comprising: providing a petroleumfluid including one or more agglomerating materials (e.g., asphaltenes,petroleum waxes, or combinations thereof); and introducing to thepetroleum fluid the petroleum additive composition of the third aspect.In some embodiments, the petroleum fluid includes crude oil or partiallyrefined crude oil.

In a seventh aspect, the disclosure provides compositions where thecompositions of the first aspect are hydraulic fracturing compositions.In some embodiments, such compositions include a major amount of water.In some embodiments, the compositions are mixed or slurried with solidparticles, such as sand particles. In some embodiments, suchcompositions include the olefinic ester compounds in amounts up to about5 percent by weight, based on the total weight of liquid ingredients inthe composition.

In an eighth aspect, the disclosure provides methods for treating a gaswell (e.g., a shale gas well or a tight gas well), including: providinga hydraulic fracturing composition according to the seventh aspect; andintroducing the hydraulic fracturing composition to a subterranean gaswell. In some embodiments, the introducing includes injecting thehydraulic fracturing composition to the subterranean gas well underhydraulic pressure.

Further aspects and embodiments are provided in the foregoing drawings,detailed description and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The following drawings are provided for purposes of illustrating variousembodiments of the compositions and methods disclosed herein. Thedrawings are provided for illustrative purposes only, and are notintended to describe any preferred compositions or preferred methods, orto serve as a source of any limitations on the scope of the claimedinventions.

FIG. 1 shows an example of an olefinic ester compound of certainembodiments disclosed herein, where R¹ is a C₉₋₁₇ alkenyl group and R²is a C₁₋₆ alkyl group.

FIG. 2 shows the results of gilsonite dissolution tests for two testcompositions against toluene.

FIG. 3 shows a rheogram for oil compositions containing an amount of thecompositions disclosed herein as an additive.

DETAILED DESCRIPTION

The following description recites various aspects and embodiments of thecompositions and methods disclosed herein. No particular embodiment isintended to define the scope of the invention. Rather, the embodimentsprovide non-limiting examples of various compositions and methods. Thedescription is to be read from the perspective of one of ordinary skillin the art. Therefore, information that is well known to the ordinarilyskilled artisan is not necessarily included.

DEFINITIONS

The following terms and phrases have the meanings indicated below,unless otherwise provided herein. This disclosure may employ other termsand phrases not expressly defined herein. Such other terms and phrasesshall have the meanings that they would possess within the context ofthis disclosure to those of ordinary skill in the art. In someinstances, a term or phrase may be defined in the singular or plural. Insuch instances, it is understood that any term in the singular mayinclude its plural counterpart and vice versa, unless expresslyindicated to the contrary.

As used herein, the singular forms “a,” “an,” and “the” include pluralreferents unless the context clearly dictates otherwise. For example,reference to “a substituent” encompasses a single substituent as well astwo or more substituents, and the like.

As used herein, “for example,” “for instance,” “such as,” or “including”are meant to introduce examples that further clarify more generalsubject matter. Unless otherwise expressly indicated, such examples areprovided only as an aid for understanding embodiments illustrated in thepresent disclosure, and are not meant to be limiting in any fashion. Nordo these phrases indicate any kind of preference for the disclosedembodiment.

As used herein, “natural oil,” “natural feedstock,” or “natural oilfeedstock” refer to oils derived from plants or animal sources. Theseterms include natural oil derivatives, unless otherwise indicated. Theterms also include modified plant or animal sources (e.g., geneticallymodified plant or animal sources), unless indicated otherwise. Examplesof natural oils include, but are not limited to, vegetable oils, algaeoils, fish oils, animal fats, tall oils, derivatives of these oils,combinations of any of these oils, and the like. Representativenon-limiting examples of vegetable oils include rapeseed oil (canolaoil), coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanutoil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil,palm kernel oil, tung oil, jatropha oil, mustard seed oil, pennycressoil, camelina oil, hempseed oil, and castor oil. Representativenon-limiting examples of animal fats include lard, tallow, poultry fat,yellow grease, and fish oil. Tall oils are by-products of wood pulpmanufacture. In some embodiments, the natural oil or natural oilfeedstock comprises one or more unsaturated glycerides (e.g.,unsaturated triglycerides). In some such embodiments, the natural oilfeedstock comprises at least 50% by weight, or at least 60% by weight,or at least 70% by weight, or at least 80% by weight, or at least 90% byweight, or at least 95% by weight, or at least 97% by weight, or atleast 99% by weight of one or more unsaturated triglycerides, based onthe total weight of the natural oil feedstock.

As used herein, “natural oil derivatives” refers to the compounds ormixtures of compounds derived from a natural oil using any one orcombination of methods known in the art. Such methods include but arenot limited to saponification, fat splitting, transesterification,esterification, hydrogenation (partial, selective, or full),isomerization, oxidation, and reduction. Representative non-limitingexamples of natural oil derivatives include gums, phospholipids,soapstock, acidulated soapstock, distillate or distillate sludge, fattyacids and fatty acid alkyl ester (e.g. non-limiting examples such as2-ethylhexyl ester), hydroxy substituted variations thereof of thenatural oil. For example, the natural oil derivative may be a fatty acidmethyl ester (“FAME”) derived from the glyceride of the natural oil. Insome embodiments, a feedstock includes canola or soybean oil, as anon-limiting example, refined, bleached, and deodorized soybean oil(i.e., RBD soybean oil). Soybean oil typically comprises about 95%weight or greater (e.g., 99% weight or greater) triglycerides of fattyacids. Major fatty acids in the polyol esters of soybean oil includesaturated fatty acids, as a non-limiting example, palmitic acid(hexadecanoic acid) and stearic acid (octadecanoic acid), andunsaturated fatty acids, as a non-limiting example, oleic acid(9-octadecenoic acid), linoleic acid (9, 12-octadecadienoic acid), andlinolenic acid (9,12,15-octadecatrienoic acid).

As used herein, “metathesis catalyst” includes any catalyst or catalystsystem that catalyzes an olefin metathesis reaction.

As used herein, “metathesize” or “metathesizing” refer to the reactingof a feedstock in the presence of a metathesis catalyst to form a“metathesized product” comprising new olefinic compounds, i.e.,“metathesized” compounds. Metathesizing is not limited to any particulartype of olefin metathesis, and may refer to cross-metathesis (i.e.,co-metathesis), self-metathesis, ring-opening metathesis, ring-openingmetathesis polymerizations (“ROMP”), ring-closing metathesis (“RCM”),and acyclic diene metathesis (“ADMET”). In some embodiments,metathesizing refers to reacting two triglycerides present in a naturalfeedstock (self-metathesis) in the presence of a metathesis catalyst,wherein each triglyceride has an unsaturated carbon-carbon double bond,thereby forming a new mixture of olefins and esters which may include atriglyceride dimer. Such triglyceride dimers may have more than oneolefinic bond, thus higher oligomers also may form. Additionally, insome other embodiments, metathesizing may refer to reacting an olefin,such as ethylene, and a triglyceride in a natural feedstock having atleast one unsaturated carbon-carbon double bond, thereby forming newolefinic molecules as well as new ester molecules (cross-metathesis).

As used herein, “hydrocarbon” refers to an organic group composed ofcarbon and hydrogen, which can be saturated or unsaturated, and caninclude aromatic groups. The term “hydrocarbyl” refers to a monovalentor polyvalent hydrocarbon moiety.

As used herein, “olefin” or “olefins” refer to compounds having at leastone unsaturated carbon-carbon double bond. In certain embodiments, theterm “olefins” refers to a group of unsaturated carbon-carbon doublebond compounds with different carbon lengths. Unless noted otherwise,the terms “olefin” or “olefins” encompasses “polyunsaturated olefins” or“poly-olefins,” which have more than one carbon-carbon double bond. Asused herein, the term “monounsaturated olefins” or “mono-olefins” refersto compounds having only one carbon-carbon double bond. A compoundhaving a terminal carbon-carbon double bond can be referred to as a“terminal olefin” or an “alpha-olefin,” while an olefin having anon-terminal carbon-carbon double bond can be referred to as an“internal olefin.” In some embodiments, the alpha-olefin is a terminalalkene, which is an alkene (as defined below) having a terminalcarbon-carbon double bond. Additional carbon-carbon double bonds can bepresent.

The number of carbon atoms in any group or compound can be representedby the terms: “C_(z)”, which refers to a group of compound having zcarbon atoms; and “C_(x-y)”, which refers to a group or compoundcontaining from x to y, inclusive, carbon atoms. For example, “C₁₋₆alkyl” represents an alkyl chain having from 1 to 6 carbon atoms and,for example, includes, but is not limited to, methyl, ethyl, n-propyl,isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl,n-pentyl, neopentyl, and n-hexyl. As a further example, a “C₄₋₁₀ alkene”refers to an alkene molecule having from 4 to 10 carbon atoms, and, forexample, includes, but is not limited to, 1-butene, 2-butene, isobutene,1-pentene, 1-hexene, 3-hexene, 1-heptene, 3-heptene, 1-octene, 4-octene,1-nonene, 4-nonene, and 1-decene.

As used herein, the term “low-molecular-weight olefin” may refer to anyone or combination of unsaturated straight, branched, or cyclichydrocarbons in the C₂₋₁₄ range. Low-molecular-weight olefins includealpha-olefins, wherein the unsaturated carbon-carbon bond is present atone end of the compound. Low-molecular-weight olefins may also includedienes or trienes. Low-molecular-weight olefins may also includeinternal olefins or “low-molecular-weight internal olefins.” In certainembodiments, the low-molecular-weight internal olefin is in the C₄₋₁₄range. Examples of low-molecular-weight olefins in the C₂₋₆ rangeinclude, but are not limited to: ethylene, propylene, 1-butene,2-butene, isobutene, 1-pentene, 2-pentene, 3-pentene, 2-methyl-1-butene,2-methyl-2-butene, 3-methyl-1-butene, cyclopentene, 1,4-pentadiene,1-hexene, 2-hexene, 3-hexene, 4-hexene, 2-methyl-1-pentene,3-methyl-1-pentene, 4-methyl-1-pentene, 2-methyl-2-pentene,3-methyl-2-pentene, 4-methyl-2-pentene, 2-methyl-3-pentene, andcyclohexene. Non-limiting examples of low-molecular-weight olefins inthe C₇₋₉ range include 1,4-heptadiene, 1-heptene, 3,6-nonadiene,3-nonene, 1,4,7-octatriene. Other possible low-molecular-weight olefinsinclude styrene and vinyl cyclohexane. In certain embodiments, it ispreferable to use a mixture of olefins, the mixture comprising linearand branched low-molecular-weight olefins in the C₄₋₁₀ range. Olefins inthe C₄₋₁₀ range can also be referred to as “short-chain olefins,” whichcan be either branched or unbranched. In one embodiments, it may bepreferable to use a mixture of linear and branched C₄ olefins (i.e.,combinations of: 1-butene, 2-butene, and/or isobutene). In otherembodiments, a higher range of C₁₁₋₁₄ may be used.

In some instances, the olefin can be an “alkene,” which refers to astraight- or branched-chain non-aromatic hydrocarbon having 2 to 30carbon atoms and one or more carbon-carbon double bonds, which may beoptionally substituted, as herein further described, with multipledegrees of substitution being allowed. A “monounsaturated alkene” refersto an alkene having one carbon-carbon double bond, while a“polyunsaturated alkene” refers to an alkene having two or morecarbon-carbon double bonds. A “lower alkene,” as used herein, refers toan alkene having from 2 to 10 carbon atoms.

As used herein, “ester” or “esters” refer to compounds having thegeneral formula: R—COO—R′, wherein R and R′ denote any organic group(such as alkyl, aryl, or silyl groups) including those bearingheteroatom-containing substituent groups. In certain embodiments, R andR′ denote alkyl, alkenyl, aryl, or alcohol groups. In certainembodiments, the term “esters” may refer to a group of compounds withthe general formula described above, wherein the compounds havedifferent carbon lengths. In certain embodiments, the esters may beesters of glycerol, which is a trihydric alcohol. The term “glyceride”can refer to esters where one, two, or three of the —OH groups of theglycerol have been esterified.

It is noted that an olefin may also comprise an ester, and an ester mayalso comprise an olefin, if the R or R′ group in the general formulaR—COO—R′ contains an unsaturated carbon-carbon double bond. Suchcompounds can be referred to as “unsaturated esters” or “olefin ester”or “olefinic ester compounds.” Further, a “terminal olefinic estercompound” may refer to an ester compound where R has an olefinpositioned at the end of the chain. An “internal olefin ester” may referto an ester compound where R has an olefin positioned at an internallocation on the chain. Additionally, the term “terminal olefin” mayrefer to an ester or an acid thereof where R′ denotes hydrogen or anyorganic compound (such as an alkyl, aryl, or silyl group) and R has anolefin positioned at the end of the chain, and the term “internalolefin” may refer to an ester or an acid thereof where R′ denoteshydrogen or any organic compound (such as an alkyl, aryl, or silylgroup) and R has an olefin positioned at an internal location on thechain.

As used herein, “acid,” “acids,” “carboxylic acid,” or “carboxylicacids” refer to compounds having the general formula: R—COOH, wherein Rdenotes any organic moiety (such as alkyl, aryl, or silyl groups),including those bearing heteroatom-containing substituent groups. Incertain embodiments, R denotes alkyl, alkenyl, aryl, or alcohol groups.In certain embodiments, the term “acids” or “carboxylic acids” may referto a group of compounds with the general formula described above,wherein the compounds have different carbon lengths.

As used herein, “alcohol” or “alcohols” refer to compounds having thegeneral formula: R—OH, wherein R denotes any organic moiety (such asalkyl, aryl, or silyl groups), including those bearingheteroatom-containing substituent groups. In certain embodiments, Rdenotes alkyl, alkenyl, aryl, or alcohol groups. In certain embodiments,the term “alcohol” or “alcohols” may refer to a group of compounds withthe general formula described above, wherein the compounds havedifferent carbon lengths. As used herein, the term “alkanol” refers toalcohols where R is an alkyl group.

As used herein, “alkyl” refers to a straight or branched chain saturatedhydrocarbon having 1 to 30 carbon atoms, which may be optionallysubstituted, as herein further described, with multiple degrees ofsubstitution being allowed. Examples of “alkyl,” as used herein,include, but are not limited to, methyl, ethyl, n-propyl, isopropyl,isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl, n-pentyl,neopentyl, n-hexyl, and 2-ethylhexyl. In some instances, the “alkyl”group can be divalent, in which case the group can alternatively bereferred to as an “alkylene” group.

As used herein, “alkenyl” refers to a straight or branched chainnon-aromatic hydrocarbon having 2 to 30 carbon atoms and having one ormore carbon-carbon double bonds, which may be optionally substituted, asherein further described, with multiple degrees of substitution beingallowed. Examples of “alkenyl,” as used herein, include, but are notlimited to, ethenyl, 2-propenyl, 2-butenyl, and 3-butenyl. In someinstances, the “alkenyl” group can be divalent, in which case the groupcan alternatively be referred to as an “alkenylene” group.

As used herein, “halogen” or “halo” refers to a fluorine, chlorine,bromine, and/or iodine atom. In some embodiments, the terms refer tofluorine and/or chlorine.

As used herein, “substituted” refers to substitution of one or morehydrogen atoms of the designated moiety with the named substituent orsubstituents, multiple degrees of substitution being allowed unlessotherwise stated, provided that the substitution results in a stable orchemically feasible compound. A stable compound or chemically feasiblecompound is one in which the chemical structure is not substantiallyaltered when kept at a temperature from about −80° C. to about +40° C.,in the absence of moisture or other chemically reactive conditions, forat least a week. As used herein, the phrases “substituted with one ormore . . . ” or “substituted one or more times . . . ” refer to a numberof substituents that equals from one to the maximum number ofsubstituents possible based on the number of available bonding sites,provided that the above conditions of stability and chemical feasibilityare met.

As used herein, “yield” refers to the amount of reaction product formedin a reaction. When expressed with units of percent (%), the term yieldrefers to the amount of reaction product actually formed, as apercentage of the amount of reaction product that would be formed if allof the limiting reactant were converted into the product.

As used herein, “mix” or “mixed” or “mixture” refers broadly to anycombining of two or more compositions. The two or more compositions neednot have the same physical state; thus, solids can be “mixed” withliquids, e.g., to form a slurry, suspension, or solution. Further, theseterms do not require any degree of homogeneity or uniformity ofcomposition. This, such “mixtures” can be homogeneous or heterogeneous,or can be uniform or non-uniform. Further, the terms do not require theuse of any particular equipment to carry out the mixing, such as anindustrial mixer.

As used herein, “hydrophilic-lipophilic balance” or “HLB,” withreference to surfactants refers to the property when determined byGriffin's method: HLB=20*(Mh/M), where Mh is the molecular weight of thehydrophilic portion of the molecule and M is the molecular weight of themolecule as a whole. Various commercial test kits can be purchased thatpermit one to measure the HLB of a surfactant by comparing theproperties of the surfactant in question with the properties of asurfactant having a known HLB value.

As used herein, “extracted fluid” refers to any hydrocarbon-containingfluid that is extracted from subterranean deposits. Extracted fluidsinclude, but are not limited to, crude oil and natural gas that isextracted from subterranean deposits.

As used herein, “petroleum wax” refers to C₁₈₊ olefins, such as thosetypically contained in extracted fluids.

As used herein, “asphaltenes” refers to fused heteroaromatic compounds,such as those typically contained in extracted fluids.

As used herein, “optionally” means that the subsequently describedevent(s) may or may not occur. In some embodiments, the optional eventdoes not occur. In some other embodiments, the optional event does occurone or more times.

As used herein, “comprise” or “comprises” or “comprising” or “comprisedof” refer to groups that are open, meaning that the group can includeadditional members in addition to those expressly recited. For example,the phrase, “comprises A” means that A must be present, but that othermembers can be present too. The terms “include,” “have,” and “composedof” and their grammatical variants have the same meaning. In contrast,“consist of” or “consists of” or “consisting of” refer to groups thatare closed. For example, the phrase “consists of A” means that A andonly A is present.

As used herein, “or” is to be given its broadest reasonableinterpretation, and is not to be limited to an either/or construction.Thus, the phrase “comprising A or B” means that A can be present and notB, or that B is present and not A, or that A and B are both present.Further, if A, for example, defines a class that can have multiplemembers, e.g., A₁ and A₂, then one or more members of the class can bepresent concurrently.

As used herein, the various functional groups represented will beunderstood to have a point of attachment at the functional group havingthe hyphen or dash (-) or an asterisk (*). In other words, in the caseof —CH₂CH₂CH₃, it will be understood that the point of attachment is theCH₂ group at the far left. If a group is recited without an asterisk ora dash, then the attachment point is indicated by the plain and ordinarymeaning of the recited group.

As used herein, multi-atom bivalent species are to be read from left toright. For example, if the specification or claims recite A-D-E and D isdefined as —OC(O)—, the resulting group with D replaced is: A-OC(O)-Eand not A-C(O)O-E.

Other terms are defined in other portions of this description, eventhough not included in this subsection.

Compositions Including Olefinic Ester Compounds

In certain aspects, the disclosure provides compositions that includeolefinic ester compounds. Any suitable olefin ester compounds can beused in the compositions. In some embodiments, the olefinic estercompounds are alkanol esters, e.g., C₁₋₆ alkanol esters, of C₁₀₋₁₈carboxylic acids having at least one carbon-carbon double bond.

Suitable alkanols include, but are not limited to, methanol, ethanol,propanol, isopropanol, butanol, isobutanol, tert-butyl alcohol,pentanol, isoamyl alcohol, neopentyl alcohol, and hexanol. In someembodiments, the alkanol is methanol, ethanol, or isopropanol. In someembodiments, the alkanol is methanol or ethanol. In some embodiments,the alkanol is methanol. Any suitable C₁₀₋₁₈ carboxylic acid can beemployed in such esters, including branched and unbranched carboxylicacids.

In some such embodiments, the olefinic ester compounds are alkanolesters of C₁₀₋₁₆ carboxylic acids having one to three carbon-carbondouble bonds, or alkanol esters of C₁₀₋₁₅ carboxylic acids having one tothree carbon-carbon double bonds, or alkanol esters of C₁₀₋₁₄ carboxylicacids having one to three carbon-carbon double bonds, or alkanol estersof C₁₀₋₁₂ carboxylic acids having one to three carbon-carbon doublebonds, or alkanol esters of C₁₂₋₁₈ carboxylic acids having one to threecarbon-carbon double bonds, or alkanol esters of C₁₂₋₁₆ carboxylic acidshaving one to three carbon-carbon double bonds, or alkanol esters ofC₁₂₋₁₅ carboxylic acids having one to three carbon-carbon double bonds,or alkanol esters of C₁₂₋₁₄ carboxylic acids having one to threecarbon-carbon double bonds. Any alkanols of the aforementionedembodiments can be used. In some embodiments, where the carboxylic acidhas two or three carbon-carbon double bonds, none of the carbon-carbondouble bands are conjugated, either to each other or to otherunsaturation in the compound. In some other embodiments, the carboxylicacid group has a single carbon-carbon double bond. In some embodiments,the carboxylic acid is 9-decenoic acid, 9-undecenoic acid, or9-dodecenoic acid.

In some embodiments, the olefinic ester compounds are methyl9-decenoate, methyl 9-undenenoate, methyl 9-dodecenoate, or a mixturethereof. In some embodiments, the olefinic ester compounds are methyl9-decenoate, methyl 9-dodecenoate, or a mixture thereof. In some otherembodiments, the olefinic ester compounds are methyl 9-decenoate. Insome other embodiments, the olefinic ester compounds are methyl9-dodecenoate.

In some embodiments, the olefinic ester compounds are one or morecompounds of formula (I):

wherein:

R¹ is C₉₋₁₇ alkenyl; and

R² is C₁₋₆ alkyl.

In some embodiments, R¹ is C₉₋₁₅ alkenyl. In some embodiments, R¹ isC₉₋₁₄ alkenyl. In some embodiments, R¹ is C₉₋₁₃ alkenyl. In someembodiments, R¹ is C₉₋₁₁ alkenyl. In some embodiments, R¹ is C₁₁₋₁₅alkenyl. In some embodiments, R¹ is C₁₁₋₁₄ alkenyl. In some embodiments,R¹ is C₁₁₋₁₃ alkenyl. In some embodiments, R¹ is C₉ alkenyl or C₁₁alkenyl. In some embodiments, R¹ is C₉ alkeny. In some embodiments, R¹is C₁₁ alkenyl. In some such embodiments, R¹ has one to threecarbon-carbon double bonds, which, when multiple carbon-carbon doublebonds are present, in some embodiments, are not conjugated. In someembodiments, R¹ has a single carbon-carbon-double bond. In some otherembodiments, R¹ has two non-conjugated double bonds. In some otherembodiments, R¹ has two or three conjugated double bonds, such as aC₁₃₋₁₅ alkenyl having two or three conjugated carbon-carbon doublebonds. In some embodiments, R¹ is —(CH₂)₇—CH═CH₂, —(CH₂)₇—CH═CH—CH₃, or—(CH₂)₇—CH═CH—CH₂—CH₃. In some embodiments, R¹ is —(CH₂)₇—CH═CH₂ or—(CH₂)₇—CH═CH—CH₂—CH₃. In some embodiments, R¹ is —(CH₂)₇—CH═CH₂. Insome embodiments, R¹ is —(CH₂)₇—CH═CH—CH₂—CH₃.

In some embodiments, R² is methyl, ethyl, isopropyl, propyl, butyl,isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, neopentyl, or hexyl.In some embodiments, R² is methyl, ethyl, isopropyl, propyl, butyl,isobutyl, sec-butyl, or tert-butyl. In some embodiments, R² is methyl,ethyl, or isopropyl. In some embodiments, R² is methyl or ethyl. In someembodiments, R² is methyl.

In some embodiments, the compositions disclosed herein consist of theolefinic ester compounds, meaning that the compositions contain no othermaterials besides the olefinic ester compounds. In some embodiments, thecompositions disclosed herein consist essentially of the olefinic estercompounds, meaning that the compositions can contain one or more othermaterials that do not materially affect the basic characteristics of theolefinic ester composition or its use. In some embodiments, thecompositions disclosed herein can comprise (or include) other materials,including materials that can affect the basic characteristics of theolefinic ester composition or its use.

The olefinic ester compounds can make up any suitable amount of thedisclosed compositions. In some embodiments, the olefinic estercompounds make up at least 50 percent by weight, or at least 60 percentby weight, or at least 70 percent by weight, or at least 80 percent byweight, or at least 90 percent by weight, or at least 95 percent byweight of the composition, based on the total weight of the composition.In some such embodiments, the olefinic ester compounds make up no morethan 99 percent by weight of the composition, based on the total weightof the composition. The compositions can include any other suitablecomponent or combination of components. In some other embodiments,however, the olefinic ester compounds make up a lower amount of thecomposition. Thus, in some embodiments, the composition includes from 1to 70 percent by weight, or from 2 to 70 percent by weight, or from 5 to70 percent by weight, or from 10 to 70 percent by weight, or from 20 to70 percent by weight, or from 30 to 70 percent by weight, or from 40 to70 percent by weight, or from 1 to 50 percent by weight, or from 2 to 50percent by weight, or from 5 to 50 percent by weight, or from 10 to 50percent by weight, or from 20 to 50 percent by weight, or from 30 to 50percent by weight, or from 1 to 30 percent by weight, or from 2 to 30percent by weight, or from 5 to 30 percent by weight, or from 10 to 30percent by weight, or from 1 to 20 percent by weight, or from 2 to 20percent by weight, or from 5 to 20 percent by weight, based on the totalweight of the composition.

In some embodiments, the compositions include one or more surfactants(according to any of the embodiments described below), such as non-ionicsurfactants, anionic surfactants, or cationic surfactants. In some suchembodiments, the compositions include one or more non-ionic surfactants.In some such embodiments, the compositions include one or more anionicsurfactants. In some such embodiments, the compositions include one ormore cationic surfactants.

In some embodiments, the olefinic ester compounds may make up a smallerportion of the composition. For example, in some embodiments, theolefinic ester compounds make up at least 1 percent by weight up to 10percent by weight, or up to 20 percent by weight, or up to 30 percent byweight, or up to 40 percent by weight, or up to 50 percent by weight, ofthe composition, based on the total weight of the composition.

In some such embodiments, the composition further comprises saturatedester compounds. For example, in some such embodiments, the saturatedester compounds make up at least 30 percent by weight, or at least 40percent by weight, up to 60 percent by weight, or up to 70 percent byweight, or up to 80 percent by weight, or up to 90 percent by weight, orup to 95 percent by weight, of the composition, based on the totalweight of the composition. As another example, the weight-to-weightratio of saturated ester compounds to olefinic ester compounds in thecomposition ranges from 1:10 to 10:1, or from 1:5 to 5:1, or from 1:3 to3:1, or from 1:2 to 2:1. Any suitable saturated fatty acid ester can beused, such as C₁₋₆ alkanolic esters of C₁₀₋₁₈ satyrated fatty acids,such as C₁₋₆ alkanolic esters (e.g., methyl esters, ethyl esters,isopropyl esters, etc.) of capric acid, lauric acid, myristic acid,palmitic acid, stearic acid, and the like.

In some instances it may be suitable to deliver the composition as acomponent of an emulsion, such as an oil-in-water emulsion or awater-in-oil emulsion. In some embodiments, the olefinic ester compoundsare part of an oily component (e.g., a primary solvent) of an emulsion,e.g., a microemulsion. In some such embodiments, the amount of primarysolvent used in the emulsion is variable with the end use. For example,in the event that the microemulsion is used to remove an undesirablesubstance from a hard surface such as, for example, stripping paint froma painted surface or removing grease from the surface of a piece ofindustrial equipment, the amount of primary solvent can be higher, suchas from 50 to 99 percent by weight, or from 60 to 99 percent by weight,or from 70 to 99 percent by weight, or from 80 to 99 percent by weight,or from 50 to 95 percent by weight, or from 60 to 95 percent by weight,or from 70 to 95 percent by weight, or from 80 to 95 percent by weight,based on the weight of the microemulsion. On the other hand, forexample, if the microemulsion is used to remove an undesirablesubstance, such as undesirable paint or graffiti, from a coated surface,such as a painted wall or railroad boxcar, the amount of primary solventmay be lower, such as from 10 to 70 percent by weight, or from 10 to 60percent by weight, or from 10 to 50 percent by weight, or from 25 to 70percent by weight, or from 25 to 60 percent by weight, or from 25 to 50percent by weight, based on the weight of the microemulsion.

In some embodiments, the relative amounts of the other components of thecomposition vary according to the end use of the composition and can beany amounts required to clean a particular undesirable substance from aparticular surface. The amount of anionic surfactant, for example, canvary from 1 to 75 percent by weight, or from 2 to 60 percent by weight,or from 3 to 50 percent by weight, or from 5 to 40 percent by weight, orfrom 5 to 30 percent by weight, or from 5 to 20 percent by weight, orfrom 5 to 14 percent by weight, or from 5 to 13 percent by weight, basedon the total weight of the composition (e.g., the undiluted,pre-emulsified composition). In some embodiments, such compositions areemulsified by mixing them with an aqueous medium to form an oil-in-wateremulsion or a water-in-oil emulsion. Suitable emulsifiers can be addedto assist in the emulsification. Any suitable degree of dilution can beused, depending on the intended end use, the desired concentration ofsolvent, and other ingredients.

Compositions comprising anionic surfactants can be used in a variety ofcleaning applications. For example, in some embodiments, compositionscomprising anionic surfactants are used for a variety of end uses.Suitable end uses include, but are not limited to, degreasing (e.g.,from various surfaces), stain removal or treatment (e.g., on fabrics orother textiles), removal of food and food-containing materials, andgeneral hard-surface cleaning. The desired end-use application mayrequire use of different surfactants or combinations of surfactants, aswell as different amounts of those surfactants.

In some embodiments, the compositions can include one or more additionalingredients or additives. Such additional ingredients or additivesinclude, but are not limited to, carriers, solvents, co-solvents (suchas longer-chain olefinic ester compounds), surfactants, co-surfactants,emulsifiers, natural or synthetic colorants, natural or syntheticfragrances, natural or synthetic deodorizers, antioxidants, corrosioninhibitors, chelating agents, precipitating and/or sequesteringbuilders, and antimicrobial agents. These agents can be used in anysuitable amounts, depending on the types of other ingredients in thecomposition (e.g., anionic surfactants, cationic surfactants, non-ionicsurfactants, etc.), the amounts of other ingredients in the composition(e.g., amount of various surfactants), whether the composition is to beformulated as an emulsion, and, if so, what type of emulsion it will be(e.g., oil-in-water, water-in-oil, etc.), and what the desired range ofend-uses will be.

In embodiments that include surfactants, any suitable surfactants can beused. For example, in some embodiments, the surfactants used in thecomposition can include surfactants having an HLB (hydrophile-lipophilebalance) of 4 to 14, or 8 to 13. In some embodiments, the surfactantsused in the composition include the amine salts (e.g., the isopropylamine salt) of dodecylbenzene sulfonic acid, the amine salts (e.g., theisopropyl amine salt) of oleic acid, linear alcohol alkoxylates,branched alcohol alkoxylates, alkyl phenol alkoxylates, fatty amides,fatty alkanolamides, fatty amine alkoxylates, sorbitan esters, glycerolesters, and combinations thereof. Other examples of suitable nonionicsurfactants include, but are not limited to, linear alcohol alkoxylates,branched alcohol alkoxylates, alkyl phenol alkoxylates, fatty amides,fatty alkanolamides, fatty amine alkoxylates, and combinations thereof.Some other examples of suitable anionic surfactants include, but are notlimited to, water-soluble salts of alkyl benzene sulfonates, alkylsulfates, alkyl polyalkoxy ether sulfates, paraffin sulfonates,alpha-olefin sulfonates and sulfosuccinates, alpha-sulfocarboxylates andtheir esters, alkyl glyceryl ether sulfonates, fatty acid monoglyceridesulfates and sulfonates, alkyl phenol polyalkoxyether sulfates andcombinations thereof. Other examples of suitable anionic surfactantsinclude, but are not limited to, the water-soluble salts or esters ofalpha-sulfonated fatty acids containing from about 6 to about 20 carbonatoms in the fatty acid group and from about 1 to about 10 carbon atomsin the ester group.

In some embodiments, such cleaning compositions can have improved high-and low-temperature stability, in comparison to a cleaning compositionnot including such a surfactant.

Surfactants can also be added to the finished composition to alleviatepotential customers of the need to select a surfactant that may besuitable for particular end uses.

Surfactant-containing compositions may also be useful in the preparationof emulsions (e.g., microemulsions or nanoemulsions), e.g., where theoily phase is emulsified in an aqueous medium, or vice versa. In suchembodiments, the surfactants can include linear alcohol alkoxylates,branched alcohol alkoxylates, alkyl phenol alkoxylates, fatty amides,fatty alkanolamides, fatty amine alkoxylates and combinations thereof.In some such embodiments, the olefinic ester compound is the primarysolvent.

In certain aspects and embodiments, such compositions can be used in acleaning method, where the cleaning composition is applied to a surface(e.g., a surface to be cleaned). In some such embodiments, the surfacecan be washed with an aqueous medium (e.g., water) after application ofthe cleaning composition.

In some embodiments, nonionic surfactants having an HLB of from about 4to about 14, or from 8 to 13, may be suitable in the preparation of amicroemulsion. Non-limiting examples of such surfactants include, butare not limited to, linear alcohol alkoxylates, branched alcoholalkoxylates, alkyl phenol alkoxylates, fatty amides, fatty amidealkoxylates, fatty amine alkoxylates and combinations thereof.

In some embodiments, cationic surfactants can be used. Suitable cationicsurfactants include, but are not limited to, water-soluble quaternaryammonium salts fatty amines, ammonium salts of fatty amines, quaternaryammonium salts of ethoxylated fatty amines, ammonium salts ofethoxylated fatty amines, quaternary ammonium salts of modified alkylpolyglucosides, and combinations thereof.

In some embodiments, the cleaning composition (e.g., a microemulsion)can include a nonionic and/or amphoteric surfactant. In some suchembodiments, the olefinic ester compound is a primary solvent.

In some embodiments, nonionic surfactants and/or amphoteric surfactantscan be used, e.g., nonionic surfactants having an HLB of from 4 to 14,or 8 to 13, e.g., in a microemulsion. Non-limiting examples of nonionicsurfactants include, but are not limited to, linear alcohol alkoxylates,branched alcohol alkoxylates, alkyl phenol alkoxylates, fatty amides,fatty amide alkoxylates, fatty amine alkoxylates and combinationsthereof. Non-limiting examples of amphoteric surfactants include, butare not limited to, water-soluble C₆₋₁₂ fatty amidoamine betaines, C₆₋₁₂fatty amidoamine sultaines and hydroxysultaines, C₆₋₁₂ fatty amidoamineoxides, fatty iminodiproponiates, C₆₋₁₂ fatty amine betaines, C₆₋₁₂fatty amines sultaines, C₆₋₁₂ fatty amine hydroxysultaines, C₆₋₁₂ fattyamine oxides, and combinations thereof.

In some embodiments, other surfactants can be used, either incombination with one or more of anionic, cationic and/or amphotericsurfactants (e.g., as short-chain co-surfactants) or alone. Non-limitingexamples of such other surfactants include, but are not limited to, C₃₋₆alcohols, glycols, glycol ethers, pyrrolidones, glycol ether esters, andcombinations thereof.

In some embodiments, the relative amounts of the components of thecomposition will vary according to the end use of the composition andcan be any amounts required to clean a particular undesirable substancefrom a particular surface. The amount of non-ionic surfactant, forexample, can vary from 1 to 75 percent by weight, or from 2 to 60percent by weight, or from 3 to 50 percent by weight, or from 5 to 40percent by weight, or from 5 to 30 percent by weight, or from 5 to 20percent by weight, based on the total weight of the composition (e.g.,the undiluted, pre-emulsified composition). In some embodiments, suchcompositions are emulsified by mixing them with an aqueous medium toform an oil-in-water emulsion or a water-in-oil emulsion. Suitableemulsifiers can be added to assist in the emulsification. Any suitabledegree of dilution can be used, depending on the intended end use, thedesired concentration of solvent, and other ingredients.

In some embodiments, the surfactants (e.g., non-ionic surfactants) canhave certain ranges of HLB values. In some embodiments, the surfactants(e.g., non-ionic surfactants) have a HLB value ranging from 4 to 10, orfrom 5 to 9, or from 6 to 8. In some embodiments, the compositioncomprises at least one non-ionic surfactant having an HLB value of about4, or an HLB value of about 5, or an HLB value of about 6, or an HLBvalue of about 7, or an HLB value of about 8, or an HLB value of about9.

In some embodiments, the surfactants (e.g., non-ionic surfactants) canhave certain ranges of molecular weights. In some embodiments, thesurfactants (e.g., non-ionic surfactants) have a molecular weightranging from 200 to 800 amu, or from 250 to 700 amu, or from 300 to 600amu. In some embodiments, the composition comprises at least onenon-ionic surfactant having a molecular weight of about 350 amu, or amolecular weight of about 400 amu, or a molecular weight of about 450amu, or a molecular weight of about 500 amu, or a molecular weight ofabout 550 amu, or a molecular weight of about 600 amu, or a molecularweight of about 650 amu.

In some embodiments, the surfactants are ethoxylated fatty acids orethoxylated alcohols. For example, in some non-limiting examples, thesurfactants are ethoxylated alcohols, where the alcohols have 8 to 16carbon atoms, or 10 to 15 carbon atoms, or 12 to 15 carbon atoms. Theethoxylated chains of such alcohols can have any suitable number ofethylene oxide units. For example, in some embodiments, the surfactantshave from 5 to 12 ethylene oxide units, or from 7 to 10 ethylene oxideunits. In some embodiments, the ethoxylated alcohols have anumber-average number of ethylene oxide units of about 5, or of about 7,or of about 9, or of about 11, or of about 12. Analogous suchethyoxylated fatty acids can be used as well.

Compositions comprising non-ionic surfactants can be used in a varietyof applications. For example, in some embodiments, compositionscomprising non-ionic surfactants are used for a variety of end uses.Suitable end uses include, but are not limited to, cleaning of equipmentused in extracting oil and gas, such as the tubing, pipes, tanks, etc.,associated with oil and gas rigs.

In some embodiments, the composition comprises water. In some suchembodiments, the composition is an emulsion, meaning that thecomposition includes two or more phases where at least one of the phasesis at least partially dispersed in one or more of the other phases. Insome further such embodiments, the composition is a microemulsion or ananoemulsion, meaning that at least one of the phases is dispersed assmall droplets whose size is on the order of about 1 nm up to about 1micron. In some embodiments, the droplet size is less than thewavelength of the lowest energy visible light, e.g., less than 350 nm,or less than 300 nm, or less than 250 nm, or less than 200 nm, or lessthan 150 nm, or less than 100 nm, down to about 50 nm.

In some other embodiments, the composition is substantially free ofwater. For example, in some embodiments, the composition includes lessthan 2 percent by weight, or less than 1 percent by weight, or less than0.5 percent by weight, or less than 0.1 percent by weight water, basedon the total weight of the composition.

In some embodiments, the composition also includes alkanol esters (e.g.,methyl esters) of saturated carboxylic acids, referred to herein as“saturated ester compounds.”

The composition can contain any suitable distribution of olefinic estercompounds. For example, in some embodiments, the composition includes atleast 50 percent by weight, or at least 60 percent by weight, or atleast 70 percent by weight, or at least 80 percent by weight alkanolesters (e.g., methyl esters) of C₁₀₋₁₂ carboxylic acids having one ormore carbon-carbon double bonds, based on the total weight of olefinicester compounds and saturated ester compounds in the composition. Insome embodiments, said C₁₀₋₁₂ carboxylic acids have one carbon-carbondouble bond. In some embodiments, the composition includes at least 50percent by weight, or at least 60 percent by weight, or at least 70percent by weight, or at least 75 percent by weight of methyl esters of9-decenoic acid, 9-undecenoic acid, or 9-dodecenoic acid, based on thetotal weight of olefinic ester compounds and saturated ester compoundsin the composition. In some embodiments, the composition includes atleast 50 percent by weight, or at least 60 percent by weight, or atleast 70 percent by weight, or at least 75 percent by weight of methylesters of 9-decenoic acid or 9-dodecenoic acid, based on the totalweight of olefinic ester compounds and saturated ester compounds in thecomposition. In some such embodiments, the composition includes no morethan 20 percent by weight, or no more than 15 percent by weight, or nomore than 10 percent by weight of saturated ester compounds, based onthe total weight of olefinic ester compounds and saturated estercompounds. In some embodiments, the composition includes: (a) 20 to 50percent by weight, or 30 to 40 percent by weight of C₁₀ olefinic estercompounds (e.g., methyl esters of 9-decenoic acid); (b) 30 to 60 percentby weight, or 40 to 50 percent by weight of C₁₂ olefinic ester compounds(e.g., methyl esters of 9-dodecenoic acid); and (c) 5 to 25 percent byweight, or 5 to 15 percent by weight of saturated ester compounds (e.g.,methyl palmitate).

In some other embodiments, the composition includes at least 40 percentby weight, or at least 50 percent by weight, or at least 60 percent byweight, or at least 70 percent by weight, or at least 80 percent byweight, or at least 90 percent by weight, or at least 95 percent byweight, of C₁₂ olefinic ester compounds (e.g., alkanol esters of9-dodecenoic acid), based on the total weight of the composition or thetotal weight of the oily phase of an oil-in-water emulsion (excludingemulsifiers). In some such embodiments, the composition includes 50 to99 percent by weight, or 60 to 99 percent by weight, of C₁₂ olefinicester compounds (e.g., alkanol esters of 9-dodecenoic acid), based onthe total weight of the composition or the total weight of the oilyphase of an oil-in-water emulsion (excluding emulsifiers).

In some such embodiments, the composition can also include variousamounts of C₁₃₋₁₅ olefinic ester compounds, e.g., alkanol esters of9,12-tridecadienoic acid, alkanol esters of 9,12-pentadecadienoic acid,and the like. In some embodiments, the composition includes up to 30percent by weight, or up to 25 percent by weight, or up to 20 percent byweight, or up to 15 percent by weight, or up to 10 percent by weight,C₁₃ olefinic ester compounds (e.g., alkanol esters of9,12-tridecanedienoic acid), based on the total weight of thecomposition or the total weight of the oily phase of an oil-in-wateremulsion (excluding emulsifiers). In some embodiments, the compositionincludes up to 35 percent by weight, or up to 30 percent by weight, orup to 25 percent by weight, or up to 20 percent by weight, or up to 15percent by weight, C₁₅ olefinic ester compounds (e.g., alkanol esters of9,12-pentadecanedienoic acid), based on the total weight of thecomposition or the total weight of the oily phase of an oil-in-wateremulsion (excluding emulsifiers).

In some such embodiments, the composition can also include an amount ofolefin, e.g., alkenes. In some embodiments, the composition includesfrom 1 to 10 percent by weight, or from 1 to 7 percent by weight,alkenes, based on the total weight of the composition or the totalweight of the oily phase of an oil-in-water emulsion (excludingemulsifiers). In some embodiments, the composition includes from 2 to 10percent by weight, or from 2 to 7 percent by weight, alkenes, based onthe total weight of the composition or the total weight of the oilyphase of an oil-in-water emulsion (excluding emulsifiers). In someembodiments, the composition includes from 3 to 10 percent by weight, orfrom 3 to 7 percent by weight, alkenes, based on the total weight of thecomposition or the total weight of the oily phase of an oil-in-wateremulsion (excluding emulsifiers).

In some other embodiments, higher amounts of saturated ester compoundscan be included in the composition. For example, in some embodiments,the composition includes at least 30 percent by weight, or at least 40percent by weight of saturated ester compounds, such as methylpalmitate, methyl stearate, methyl laurate, etc., based on the totalweight of olefinic ester compounds and saturated ester compounds in thecomposition. In some such embodiments, the amounts of C₁₀₋₁₂ unsaturatedester compounds can be lower. For example, in some embodiments, thecomposition includes no more than 50 percent by weight, or no more than40 percent by weight, or no more than 35 percent by weight of C₁₀₋₁₂unsaturated ester compounds (e.g., methyl 9-decenoate and methyl9-dodecenoate). In some embodiments, the composition includes: (a) 5 to30 percent by weight, or 5 to 20 percent by weight of C₁₀ olefinic estercompounds (e.g., methyl esters of 9-decenoic acid); (b) 5 to 30 percentby weight, or 10 to 20 percent by weight of C₁₂ olefinic ester compounds(e.g., methyl esters of 9-dodecenoic acid); and (c) 30 to 70 percent byweight, or 40 to 60 percent by weight of saturated ester compounds(e.g., methyl palmitate).

In some other embodiments, the composition includes at least 20 percentby weight, or at least 30 percent by weight, or at least 40 percent byweight of terminal olefinic ester compounds, based on the total weightof olefinic ester compounds in the composition. In some otherembodiments, the composition includes no more than 30 percent by weight,or no more than 40 percent by weight, or no more than 50 percent byweight of terminal olefinic ester compounds, based on the total weightof olefinic ester compounds in the composition.

In some embodiments, the composition can include at least 50% by weight,or at least 60% by weight, or at least 70% by weight, or at least 80% byweight, of C₁₀₋₁₂ unsaturated ester compounds (e.g., methyl 9-decenoateand methyl 9-dodecenoate), as well as a ketone, such as cyclohexanone,e.g., in an amount of up to 5% by weight, or up to 10% by weight, or upto 15% by weight, or up to 20% by weight, based on the total weight ofthe composition. Such compositions can also include, in someembodiments, other fatty acids, such as oleic acid. In some embodiments,the composition can also include certain petroleum distillates, such asmineral oil (100 SUS).

Derivation from Renewable Sources

The olefinic ester compounds employed in any of the aspects orembodiments disclosed herein can, in certain embodiments, be derivedfrom renewable sources, such as from various natural oils or theirderivatives. Any suitable methods can be used to make these compoundsfrom such renewable sources. Suitable methods include, but are notlimited to, fermentation, conversion by bioorganisms, and conversion bymetathesis.

Olefin metathesis provides one possible means to convert certain naturaloil feedstocks into olefins and esters that can be used in a variety ofapplications, or that can be further modified chemically and used in avariety of applications. In some embodiments, a composition (orcomponents of a composition) may be formed from a renewable feedstock,such as a renewable feedstock formed through metathesis reactions ofnatural oils and/or their fatty acid or fatty ester derivatives. Whencompounds containing a carbon-carbon double bond undergo metathesisreactions in the presence of a metathesis catalyst, some or all of theoriginal carbon-carbon double bonds are broken, and new carbon-carbondouble bonds are formed. The products of such metathesis reactionsinclude carbon-carbon double bonds in different locations, which canprovide unsaturated organic compounds having useful chemical properties.

A wide range of natural oils, or derivatives thereof, can be used insuch metathesis reactions. Examples of suitable natural oils include,but are not limited to, vegetable oils, algae oils, fish oils, animalfats, tall oils, derivatives of these oils, combinations of any of theseoils, and the like. Representative non-limiting examples of vegetableoils include rapeseed oil (canola oil), coconut oil, corn oil,cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesameoil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil,jatropha oil, mustard seed oil, pennycress oil, camelina oil, hempseedoil, and castor oil. Representative non-limiting examples of animal fatsinclude lard, tallow, poultry fat, yellow grease, and fish oil. Talloils are by-products of wood pulp manufacture. In some embodiments, thenatural oil or natural oil feedstock comprises one or more unsaturatedglycerides (e.g., unsaturated triglycerides). In some such embodiments,the natural oil feedstock comprises at least 50% by weight, or at least60% by weight, or at least 70% by weight, or at least 80% by weight, orat least 90% by weight, or at least 95% by weight, or at least 97% byweight, or at least 99% by weight of one or more unsaturatedtriglycerides, based on the total weight of the natural oil feedstock.

The natural oil may include canola or soybean oil, such as refined,bleached and deodorized soybean oil (i.e., RBD soybean oil). Soybean oiltypically includes about 95 percent by weight (wt %) or greater (e.g.,99 wt % or greater) triglycerides of fatty acids. Major fatty acids inthe polyol esters of soybean oil include but are not limited tosaturated fatty acids such as palmitic acid (hexadecanoic acid) andstearic acid (octadecanoic acid), and unsaturated fatty acids such asoleic acid (9-octadecenoic acid), linoleic acid (9,12-octadecadienoicacid), and linolenic acid (9,12,15-octadecatrienoic acid).

Metathesized natural oils can also be used. Examples of metathesizednatural oils include but are not limited to a metathesized vegetableoil, a metathesized algal oil, a metathesized animal fat, a metathesizedtall oil, a metathesized derivatives of these oils, or mixtures thereof.For example, a metathesized vegetable oil may include metathesizedcanola oil, metathesized rapeseed oil, metathesized coconut oil,metathesized corn oil, metathesized cottonseed oil, metathesized oliveoil, metathesized palm oil, metathesized peanut oil, metathesizedsafflower oil, metathesized sesame oil, metathesized soybean oil,metathesized sunflower oil, metathesized linseed oil, metathesized palmkernel oil, metathesized tung oil, metathesized jatropha oil,metathesized mustard oil, metathesized camelina oil, metathesizedpennycress oil, metathesized castor oil, metathesized derivatives ofthese oils, or mixtures thereof. In another example, the metathesizednatural oil may include a metathesized animal fat, such as metathesizedlard, metathesized tallow, metathesized poultry fat, metathesized fishoil, metathesized derivatives of these oils, or mixtures thereof.

Such natural oils, or derivatives thereof, can contain esters, such astriglycerides, of various unsaturated fatty acids. The identity andconcentration of such fatty acids varies depending on the oil source,and, in some cases, on the variety. In some embodiments, the natural oilcomprises one or more esters of oleic acid, linoleic acid, linolenicacid, or any combination thereof. When such fatty acid esters aremetathesized, new compounds are formed. For example, in embodimentswhere the metathesis uses certain short-chain olefins, e.g., ethylene,propylene, or 1-butene, and where the natural oil includes esters ofoleic acid, an amount of 1-decene and 1-decenoid acid (or an esterthereof), among other products, are formed. Followingtransesterification, for example, with an alkyl alcohol, an amount of9-denenoic acid alkyl ester is formed. In some such embodiments, aseparation step may occur between the metathesis and thetransesterification, where the alkenes are separated from the esters. Insome other embodiments, transesterification can occur before metathesis,and the metathesis is performed on the transesterified product.

In some embodiments, the natural oil can be subjected to variouspre-treatment processes, which can facilitate their utility for use incertain metathesis reactions. Useful pre-treatment methods are describedin United States Patent Application Publication Nos. 2011/0113679,2014/0275681, and 2014/0275595, all three of which are herebyincorporated by reference as though fully set forth herein.

In some embodiments, after any optional pre-treatment of the natural oilfeedstock, the natural oil feedstock is reacted in the presence of ametathesis catalyst in a metathesis reactor. In some other embodiments,an unsaturated ester (e.g., an unsaturated glyceride, such as anunsaturated triglyceride) is reacted in the presence of a metathesiscatalyst in a metathesis reactor. These unsaturated esters may be acomponent of a natural oil feedstock, or may be derived from othersources, e.g., from esters generated in earlier-performed metathesisreactions. In certain embodiments, in the presence of a metathesiscatalyst, the natural oil or unsaturated ester can undergo aself-metathesis reaction with itself. In other embodiments, the naturaloil or unsaturated ester undergoes a cross-metathesis reaction with thelow-molecular-weight olefin or mid-weight olefin. The self-metathesisand/or cross-metathesis reactions form a metathesized product whereinthe metathesized product comprises olefins and esters.

In some embodiments, the low-molecular-weight olefin (or short-chainolefin) is in the C₂₋₆ range. As a non-limiting example, in oneembodiment, the low-molecular-weight olefin may comprise at least oneof: ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene,2-pentene, 3-pentene, 2-methyl-1-butene, 2-methyl-2-butene,3-methyl-1-butene, cyclopentene, 1,4-pentadiene, 1-hexene, 2-hexene,3-hexene, 4-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene,4-methyl-2-pentene, 2-methyl-3-pentene, and cyclohexene. In someembodiments, the short-chain olefin is 1-butene. In some instances, ahigher-molecular-weight olefin can also be used.

In some embodiments, the metathesis comprises reacting a natural oilfeedstock (or another unsaturated ester) in the presence of a metathesiscatalyst. In some such embodiments, the metathesis comprises reactingone or more unsaturated glycerides (e.g., unsaturated triglycerides) inthe natural oil feedstock in the presence of a metathesis catalyst. Insome embodiments, the unsaturated glyceride comprises one or more estersof oleic acid, linoleic acid, linoleic acid, or combinations thereof. Insome other embodiments, the unsaturated glyceride is the product of thepartial hydrogenation and/or the metathesis of another unsaturatedglyceride (as described above). In some such embodiments, the metathesisis a cross-metathesis of any of the aforementioned unsaturatedtriglyceride species with another olefin, e.g., an alkene. In some suchembodiments, the alkene used in the cross-metathesis is a lower alkene,such as ethylene, propylene, 1-butene, 2-butene, etc. In someembodiments, the alkene is ethylene. In some other embodiments, thealkene is propylene. In some further embodiments, the alkene is1-butene. And in some even further embodiments, the alkene is 2-butene.

Metathesis reactions can provide a variety of useful products, whenemployed in the methods disclosed herein. For example, the unsaturatedesters may be derived from a natural oil feedstock, in addition to othervaluable compositions. Moreover, in some embodiments, a number ofvaluable compositions can be targeted through the self-metathesisreaction of a natural oil feedstock, or the cross-metathesis reaction ofthe natural oil feedstock with a low-molecular-weight olefin ormid-weight olefin, in the presence of a metathesis catalyst. Suchvaluable compositions can include fuel compositions, detergents,surfactants, and other specialty chemicals. Additionally,transesterified products (i.e., the products formed fromtransesterifying an ester in the presence of an alcohol) may also betargeted, non-limiting examples of which include: fatty acid methylesters (“FAMEs”); biodiesel; 9-decenoic acid (“9DA”) esters,9-undecenoic acid (“9UDA”) esters, and/or 9-dodecenoic acid (“9DDA”)esters; 9DA, 9UDA, and/or 9DDA; alkali metal salts and alkaline earthmetal salts of 9DA, 9UDA, and/or 9DDA; dimers of the transesterifiedproducts; and mixtures thereof.

Further, in some embodiments, multiple metathesis reactions can also beemployed. In some embodiments, the multiple metathesis reactions occursequentially in the same reactor. For example, a glyceride containinglinoleic acid can be metathesized with a terminal lower alkene (e.g.,ethylene, propylene, 1-butene, and the like) to form 1,4-decadiene,which can be metathesized a second time with a terminal lower alkene toform 1,4-pentadiene. In other embodiments, however, the multiplemetathesis reactions are not sequential, such that at least one otherstep (e.g., transesterification, hydrogenation, etc.) can be performedbetween the first metathesis step and the following metathesis step.These multiple metathesis procedures can be used to obtain products thatmay not be readily obtainable from a single metathesis reaction usingavailable starting materials. For example, in some embodiments, multiplemetathesis can involve self-metathesis followed by cross-metathesis toobtain metathesis dimers, trimmers, and the like. In some otherembodiments, multiple metathesis can be used to obtain olefin and/orester components that have chain lengths that may not be achievable froma single metathesis reaction with a natural oil triglyceride and typicallower alkenes (e.g., ethylene, propylene, 1-butene, 2-butene, and thelike). Such multiple metathesis can be useful in an industrial-scalereactor, where it may be easier to perform multiple metathesis than tomodify the reactor to use a different alkene.

The conditions for such metathesis reactions, and the reactor design,and suitable catalysts are as described above with reference to themetathesis of the olefin esters. That discussion is incorporated byreference as though fully set forth herein.

In the embodiments above, the natural oil (e.g., as a glyceride) ismetathesized, followed by transesterification. In some otherembodiments, transesterification can precede metathesis, such that thefatty acid esters subjected to metathesis are fatty acid esters ofmonohydric alcohols, such as methanol, ethanol, or isopropanol.

Olefin Metathesis

In some embodiments, one or more of the unsaturated monomers can be madeby metathesizing a natural oil or natural oil derivative. The terms“metathesis” or “metathesizing” can refer to a variety of differentreactions, including, but not limited to, cross-metathesis,self-metathesis, ring-opening metathesis, ring-opening metathesispolymerizations (“ROMP”), ring-closing metathesis (“RCM”), and acyclicdiene metathesis (“ADMET”). Any suitable metathesis reaction can beused, depending on the desired product or product mixture.

In some embodiments, after any optional pre-treatment of the natural oilfeedstock, the natural oil feedstock is reacted in the presence of ametathesis catalyst in a metathesis reactor. In some other embodiments,an unsaturated ester (e.g., an unsaturated glyceride, such as anunsaturated triglyceride) is reacted in the presence of a metathesiscatalyst in a metathesis reactor. These unsaturated esters may be acomponent of a natural oil feedstock, or may be derived from othersources, e.g., from esters generated in earlier-performed metathesisreactions. In certain embodiments, in the presence of a metathesiscatalyst, the natural oil or unsaturated ester can undergo aself-metathesis reaction with itself. In other embodiments, the naturaloil or unsaturated ester undergoes a cross-metathesis reaction with thelow-molecular-weight olefin or mid-weight olefin. The self-metathesisand/or cross-metathesis reactions form a metathesized product whereinthe metathesized product comprises olefins and esters.

In some embodiments, the low-molecular-weight olefin is in the C₂₋₆range. As a non-limiting example, in one embodiment, thelow-molecular-weight olefin may comprise at least one of: ethylene,propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene,3-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene,cyclopentene, 1,4-pentadiene, 1-hexene, 2-hexene, 3-hexene, 4-hexene,2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene,2-methyl-3-pentene, and cyclohexene. In some instances, ahigher-molecular-weight olefin can also be used.

In some embodiments, the metathesis comprises reacting a natural oilfeedstock (or another unsaturated ester) in the presence of a metathesiscatalyst. In some such embodiments, the metathesis comprises reactingone or more unsaturated glycerides (e.g., unsaturated triglycerides) inthe natural oil feedstock in the presence of a metathesis catalyst. Insome embodiments, the unsaturated glyceride comprises one or more estersof oleic acid, linoleic acid, linoleic acid, or combinations thereof. Insome other embodiments, the unsaturated glyceride is the product of thepartial hydrogenation and/or the metathesis of another unsaturatedglyceride (as described above). In some such embodiments, the metathesisis a cross-metathesis of any of the aforementioned unsaturatedtriglyceride species with another olefin, e.g., an alkene. In some suchembodiments, the alkene used in the cross-metathesis is a lower alkene,such as ethylene, propylene, 1-butene, 2-butene, etc. In someembodiments, the alkene is ethylene. In some other embodiments, thealkene is propylene. In some further embodiments, the alkene is1-butene. And in some even further embodiments, the alkene is 2-butene.

Metathesis reactions can provide a variety of useful products, whenemployed in the methods disclosed herein. For example, terminal olefinsand internal olefins may be derived from a natural oil feedstock, inaddition to other valuable compositions. Moreover, in some embodiments,a number of valuable compositions can be targeted through theself-metathesis reaction of a natural oil feedstock, or thecross-metathesis reaction of the natural oil feedstock with alow-molecular-weight olefin or mid-weight olefin, in the presence of ametathesis catalyst. Such valuable compositions can include fuelcompositions, detergents, surfactants, and other specialty chemicals.Additionally, transesterified products (i.e., the products formed fromtransesterifying an ester in the presence of an alcohol) may also betargeted, non-limiting examples of which include: fatty acid methylesters (“FAMEs”); biodiesel; 9-decenoic acid (“9DA”) esters,9-undecenoic acid (“9UDA”) esters, and/or 9-dodecenoic acid (“9DDA”)esters; 9DA, 9UDA, and/or 9DDA; alkali metal salts and alkaline earthmetal salts of 9DA, 9UDA, and/or 9DDA; dimers of the transesterifiedproducts; and mixtures thereof.

Further, in some embodiments, the methods disclosed herein can employmultiple metathesis reactions. In some embodiments, the multiplemetathesis reactions occur sequentially in the same reactor. Forexample, a glyceride containing linoleic acid can be metathesized with aterminal lower alkene (e.g., ethylene, propylene, 1-butene, and thelike) to form 1,4-decadiene, which can be metathesized a second timewith a terminal lower alkene to form 1,4-pentadiene. In otherembodiments, however, the multiple metathesis reactions are notsequential, such that at least one other step (e.g.,transesterification, hydrogenation, etc.) can be performed between thefirst metathesis step and the following metathesis step. These multiplemetathesis procedures can be used to obtain products that may not bereadily obtainable from a single metathesis reaction using availablestarting materials. For example, in some embodiments, multiplemetathesis can involve self-metathesis followed by cross-metathesis toobtain metathesis dimers, trimmers, and the like. In some otherembodiments, multiple metathesis can be used to obtain olefin and/orester components that have chain lengths that may not be achievable froma single metathesis reaction with a natural oil triglyceride and typicallower alkenes (e.g., ethylene, propylene, 1-butene, 2-butene, and thelike). Such multiple metathesis can be useful in an industrial-scalereactor, where it may be easier to perform multiple metathesis than tomodify the reactor to use a different alkene.

The metathesis process can be conducted under any conditions adequate toproduce the desired metathesis products. For example, stoichiometry,atmosphere, solvent, temperature, and pressure can be selected by oneskilled in the art to produce a desired product and to minimizeundesirable byproducts. In some embodiments, the metathesis process maybe conducted under an inert atmosphere. Similarly, in embodiments wherea reagent is supplied as a gas, an inert gaseous diluent can be used inthe gas stream. In such embodiments, the inert atmosphere or inertgaseous diluent typically is an inert gas, meaning that the gas does notinteract with the metathesis catalyst to impede catalysis to asubstantial degree. For example, non-limiting examples of inert gasesinclude helium, neon, argon, and nitrogen, used individually or in witheach other and other inert gases.

The rector design for the metathesis reaction can vary depending on avariety of factors, including, but not limited to, the scale of thereaction, the reaction conditions (heat, pressure, etc.), the identityof the catalyst, the identity of the materials being reacted in thereactor, and the nature of the feedstock being employed. Suitablereactors can be designed by those of skill in the art, depending on therelevant factors, and incorporated into a refining process such, such asthose disclosed herein.

The metathesis reactions disclosed herein generally occur in thepresence of one or more metathesis catalysts. Such methods can employany suitable metathesis catalyst. The metathesis catalyst in thisreaction may include any catalyst or catalyst system that catalyzes ametathesis reaction. Any known metathesis catalyst may be used, alone orin combination with one or more additional catalysts. Examples ofmetathesis catalysts and process conditions are described in US2011/0160472, incorporated by reference herein in its entirety, exceptthat in the event of any inconsistent disclosure or definition from thepresent specification, the disclosure or definition herein shall bedeemed to prevail. A number of the metathesis catalysts described in US2011/0160472 are presently available from Materia, Inc. (Pasadena,Calif.).

In some embodiments, the metathesis catalyst includes a Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes a first-generationGrubbs-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes asecond-generation Grubbs-type olefin metathesis catalyst and/or anentity derived therefrom. In some embodiments, the metathesis catalystincludes a first-generation Hoveyda-Grubbs-type olefin metathesiscatalyst and/or an entity derived therefrom. In some embodiments, themetathesis catalyst includes a second-generation Hoveyda-Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes one or a plurality of theruthenium carbene metathesis catalysts sold by Materia, Inc. ofPasadena, Calif. and/or one or more entities derived from suchcatalysts. Representative metathesis catalysts from Materia, Inc. foruse in accordance with the present teachings include but are not limitedto those sold under the following product numbers as well ascombinations thereof: product no. C823 (CAS no. 172222-30-9), productno. C848 (CAS no. 246047-72-3), product no. C601 (CAS no. 203714-71-0),product no. C627 (CAS no. 301224-40-8), product no. C571 (CAS no.927429-61-6), product no. C598 (CAS no. 802912-44-3), product no. C793(CAS no. 927429-60-5), product no. C801 (CAS no. 194659-03-9), productno. C827 (CAS no. 253688-91-4), product no. C884 (CAS no. 900169-53-1),product no. C833 (CAS no. 1020085-61-3), product no. C859 (CAS no.832146-68-6), product no. C711 (CAS no. 635679-24-2), product no. C933(CAS no. 373640-75-6).

In some embodiments, the metathesis catalyst includes a molybdenumand/or tungsten carbene complex and/or an entity derived from such acomplex. In some embodiments, the metathesis catalyst includes aSchrock-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes ahigh-oxidation-state alkylidene complex of molybdenum and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesa high-oxidation-state alkylidene complex of tungsten and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesmolybdenum (VI). In some embodiments, the metathesis catalyst includestungsten (VI). In some embodiments, the metathesis catalyst includes amolybdenum- and/or a tungsten-containing alkylidene complex of a typedescribed in one or more of (a) Angew. Chem. Int. Ed. Engl., 2003, 42,4592-4633; (b) Chem. Rev., 2002, 102, 145-179; and/or (c) Chem. Rev.,2009, 109, 3211-3226, each of which is incorporated by reference hereinin its entirety, except that in the event of any inconsistent disclosureor definition from the present specification, the disclosure ordefinition herein shall be deemed to prevail.

In certain embodiments, the metathesis catalyst is dissolved in asolvent prior to conducting the metathesis reaction. In certain suchembodiments, the solvent chosen may be selected to be substantiallyinert with respect to the metathesis catalyst. For example,substantially inert solvents include, without limitation: aromatichydrocarbons, such as benzene, toluene, xylenes, etc.; halogenatedaromatic hydrocarbons, such as chlorobenzene and dichlorobenzene;aliphatic solvents, including pentane, hexane, heptane, cyclohexane,etc.; and chlorinated alkanes, such as dichloromethane, chloroform,dichloroethane, etc. In some embodiments, the solvent comprises toluene.

In other embodiments, the metathesis catalyst is not dissolved in asolvent prior to conducting the metathesis reaction. The catalyst,instead, for example, can be slurried with the natural oil orunsaturated ester, where the natural oil or unsaturated ester is in aliquid state. Under these conditions, it is possible to eliminate thesolvent (e.g., toluene) from the process and eliminate downstream olefinlosses when separating the solvent. In other embodiments, the metathesiscatalyst may be added in solid state form (and not slurried) to thenatural oil or unsaturated ester (e.g., as an auger feed).

The metathesis reaction temperature may, in some instances, be arate-controlling variable where the temperature is selected to provide adesired product at an acceptable rate. In certain embodiments, themetathesis reaction temperature is greater than −40° C., or greater than−20° C., or greater than 0° C., or greater than 10° C. In certainembodiments, the metathesis reaction temperature is less than 200° C.,or less than 150° C., or less than 120° C. In some embodiments, themetathesis reaction temperature is between 0° C. and 150° C., or isbetween 10° C. and 120° C.

The metathesis reaction can be run under any desired pressure. In someinstances, it may be desirable to maintain a total pressure that is highenough to keep the cross-metathesis reagent in solution. Therefore, asthe molecular weight of the cross-metathesis reagent increases, thelower pressure range typically decreases since the boiling point of thecross-metathesis reagent increases. The total pressure may be selectedto be greater than 0.1 atm (10 kPa), or greater than 0.3 atm (30 kPa),or greater than 1 atm (100 kPa). In some embodiments, the reactionpressure is no more than about 70 atm (7000 kPa), or no more than about30 atm (3000 kPa). In some embodiments, the pressure for the metathesisreaction ranges from about 1 atm (100 kPa) to about 30 atm (3000 kPa).

Cleaning Compositions and Methods of Use

In certain aspects, the disclosed compositions are cleaningcompositions, such as compositions useful for cleaning materials and/ordeposits that contain petroleum waxes (e.g., macrocrystalline and/ormicrocrystalline waxes) and/or asphaltenes. Such materials oftenaccumulate on equipment associated with the extraction and/or transportof extracted fluids, such as oil and gas. Therefore, in someembodiments, the compositions disclosed herein are useful for cleaningvarious surfaces on oil and/or gas rigs (e.g., tubing, pipes, tanks, andthe like) and various mechanical devices (e.g., gauges, valves,regulators, and the like). In some embodiments, the compositionsdisclosed herein are useful for cleaning various surfaces of equipmentused to transport oil and gas, such as pipes.

In certain aspects, the disclosure provides methods for cleaning asurface, comprising: providing a surface having a material and/or adeposit disposed thereon, the material and/or deposit comprisingasphtaltenes, petroleum waxes, or a combination thereof; and contactingthe material and/or deposit with any of the compositions disclosedherein. In some embodiments, the surface is a surface of a rig, such asan oil rig (e.g., on-land drilling rig or off-shore drilling platform).In some such embodiments, the surface is the interior wall of a pipe,the interior wall of a tank, the interior wall of a tube, or a surfaceof a piece of mechanical equipment, such as a gauge, valve, orregulator. In some embodiments, the materials and/or deposit comprisesasphaltehes. In some embodiments, the material and/or deposit comprisespetroleum waxes, such as macrocrystalline waxes (paraffin waxes) and/ormicrocrystalline waxes.

The cleaning capability of the compositions is not limited to anyparticular type of surface, including both hard and porous surfaces. Thecompositions can be used effectively on a variety of surfaces,including, but not limited to, plastics, other polymeric materials,metals, wood, glass, ceramic, rock (e.g., granite, marble, etc.), andvarious synthetic countertop materials.

In some embodiments, an effective amount or a cleaning-effective amountof the composition is used. This amount can be determined readily basedon the particular application, based on factors such as the nature ofthe surface, the nature and/or amount of the material to be removed, andthe like.

Reducing Agglomeration in a Petroleum Fluid

In certain aspects, the disclosed compositions are petroleum additivecompositions, meaning that they are added to a petroleum fluid (e.g.,crude oil or partially refined crude oil), optionally with othermaterials. In some embodiments, the compositions are added for thepurpose of preventing or inhibiting the development of variousagglomerates in the petroleum fluid. Such agglomerates include, but arenot limited to, materials that include asphaltenes, petroleum waxes(macrocrystalline waxes and/or microcrystalline waxes), or combinationsthereof. The additive compositions can be present in any suitableamount. In some embodiments, the petroleum fluid nevertheless makes up amajor portion of the resulting composition. For example, in someembodiments, the petroleum fluid makes up at least 80 percent by weight,or at least 90 percent by weight, or at least 95 percent by weight, orat least 97 percent by weight, or at least 98 percent by weight, or atleast 99 percent by weight of the petroleum composition, based on thetotal weight of the petroleum composition. In some embodiments, thepetroleum additive composition makes up no more than 5 percent byweight, or no more than 3 percent by weight, or no more than 2 percentby weight, or no more than 1 percent by weight, of the petroleumcomposition, based on the total weight of the petroleum composition.

In certain aspects, the disclosure provides methods for reducingagglomerates (e.g., reducing agglomerate formation) in a petroleumfluid, comprising: providing a petroleum fluid comprising one or moreagglomerating materials, the agglomerating materials comprisingasphaltenes, petroleum waxes, or a combination thereof; and introducingto the petroleum fluid the petroleum additive composition of any of theembodiments disclosed herein, e.g., to form a treated petroleum fluid.In some embodiments, the introducing comprises adding the petroleumadditive composition to the petroleum fluid in an amount such that thepetroleum additive composition makes up no more than 5 percent byweight, or no more than 3 percent by weight, or no more than 2 percentby weight, or no more than 1 percent by weight, of the treated petroleumcomposition, based on the total weight of the treated petroleumcomposition. In some embodiments, the petroleum fluid comprises crudeoil or a partially refined crude oil. In some embodiments, the one ormore agglomerating materials comprise asphaltenes. In some embodiments,the one or more agglomerating materials petroleum waxes, such asmacrocrystalline waxes, microcrystalline waxes, or combinations thereof.

In some embodiments, an effective amount or anagglomerate-reducing-effective amount of the composition is used. Thisamount can be determined readily based on the particular application,based on factors such as the nature of the petroleum fluid, and thenature and/or amount of the agglomerating materials present in thepetroleum fluid.

Compositions for Hydraulic Fracturing and Use Thereof

In certain aspects, the disclosed compositions are suitable for use ashydraulic fracturing fluids. In some such embodiments, the compositionsare suitable for injection into a subterranean gas well (e.g., underhydraulic pressure) to create fractures through which natural gas (or,in some instances, oil) can flow. Such gas is often referred to as shalegas, tight gas, etc. In some embodiments, such compositions include amajor amount of water. For example, in some embodiments, thecompositions include at least 50 percent by weight, or at least 60percent by weight, or at least 70 percent by weight, or at least 80percent by weight, or at least 90 percent by weight, or at least 95percent by weight, water, based on the total weight of liquidingredients in the composition. In some embodiments, such liquidcompositions are mixed or slurried with solid components, such as sand.The compositions can include any suitable amount of the olefinic estercompositions of any of the above embodiments. For example, in someembodiments, the compositions include up to 5 percent by weight, or upto 3 percent by weight, or up to 2 percent by weight, or up to 1 percentby weight, or up to 0.5 percent by weight, of olefinic ester compounds,based on the total weight of liquid ingredients in the composition. Inany of the aforementioned embodiments, the compositions include at least0.01 percent by weight, or at least 0.05 percent by weight, or at least0.1 percent by weight, of olefinic ester compounds, based on the totalweight of liquid ingredients in the composition.

In certain aspects, the disclosure provides methods for treating a gaswell, including: providing a hydraulic fracturing composition accordingto the above embodiments, which is optionally mixed or slurried withsolid particles (e.g., sand particles); and introducing the hydraulicfracturing composition into a subterranean gas well, e.g., injectingunder hydraulic pressure.

EXAMPLES Example 1 Sample Preparation

Four compositions were prepared. Composition 1A included methyl9-decenoate in its substantially pure form (>97 wt % pure). Composition1B included methyl 9-dodecenoate in its substantially pure form (>97 wt% pure). Composition 1C included: 33.0 wt % methyl 9-decenoate; 46.9 wt% methyl 9-dodecenoate; 1.6 wt %

C₁₃ olefinic methyl ester; 2.2 wt % methyl myristate; 4.1 wt % C₁₅olefinic methyl ester; 8.0 wt % methyl palmitate; 1.2 wt % alkenes; andtrace amounts of other ingredients. Composition 1D included: 11.9 wt %methyl 9-decenoate; 18.6 wt % methyl 9-dodecenoate; 1.7 wt % C₁₃olefinic methyl ester; 0.1 wt % methyl myristate; 3.7 wt % C₁₅ olefinicmethyl ester; 48.8 wt % methyl palmitate; 7.8 wt % methyl stearate; 5.3wt % dimethyl 9-octadecenedioate; 1.2 wt % alkenes; and trace amounts ofother ingredients. In instances where the samples contain more than oneingredient, the samples were mixed to ensure homogeneity.

Example 2 Solvency

Solvency power was determined by calculating kauri-butanol (K_(b))values (ASTM D1133) for Compositions 1A-1D. The K_(b) values werecalculated according to ASTM D1133, which is incorporated herein byreference. A butanolic solution of kauri resin was titrated with eachcomposition until the admixture reaches a certain turbidity. Highervalues correlate with improved performance as a solvent. Table 1 showsthe measured K_(b) values for Compositions 1A-1D. K_(b) values were alsomeasured for certain other solvents as a basis of comparison.

TABLE 1 Solvent K_(b) Value Composition 1A 98.5 Composition 1B 85.0Composition 1C 81.5 Composition 1D 63.5 Methyl Caprate 96.1 MethylLaurate 77.0 Methyl Soyate 59.3 Methyl Caprylate/Caprate 112.0

Example 3 Bitumen Removal

Bitumen is a composite mixture of relatively high-molecular-weighthydrocarbons, maltenes, and asphaltenes, all of which are present incrude oil. Bitumen is therefore a representative composition of certaindeposits that may develop in oil wells, and that may need to be cleanedaway by the use of certain solvents. Bitumen removal was measuredaccording to ASTM D4488-95 A5, which is incorporated herein byreference, for each of the compositions as well as methyl soyate andd-limonene (as a comparison). Bitumen removal was measured in terms ofthe number of Gardner scrub cycles necessary to achieve at least 80%removal. Lower values correlate with improved performance. Results areshown in Table 2.

TABLE 2 Solvent Gardner Scrub Cycles 80% Removal Composition 1A 55Composition 1B 45 Composition 1C 60 Composition 1D 105 Methyl Soyate 175D-Limonene 30

Example 4 Asphaltene & Rig Wash Removal Compositions

Various asphaltene and rig wash removal formulations were made usingComposition 1B. Such compositions can be useful for oil/gas well-relatedapplications, especially for breaking up asphaltene deposits or washingabove-the ground equipment. Table 3 shows the makeup of variouscompositions (in percent by weight). It should also be noted, thecompositions identified as Composition 1B may, in certain optionalembodiments, include some small amount of deodorizer. The compositionsare described as 2A to 2G.

TABLE 3 Ingredient 2A 2B 2C 2D 2E 2F 2G Composition 1B 59.9 85.0 60.025.0 31.0 24.0 32.0 POLARTECH LA 8005 8.5 — — ACTRASOL MY-75 17.0TOMADOL 25-9 7.0 7.0 BIOSOFT N1-9 — — — 15.0 23.0 18.0 BIOSOFT N411 — —— 38.0 46.0 37.0 BIOSOFT N300 58.0 BIOSOFT N91-6 10.0 STEPANOL AM — — —22.0 ALCOSPERSE 747 21.0 Cyclohexanone 12.7 5.0 5.0 Oleic Acid 0.9 3.03.0 KOH (45% in H₂0 soln.) 1.0 — — Mineral Oil (100 SUS) — — 20.0Benzene sulfonic acid — — 5.0 POLARTECH products are supplied by AftonChemical Corp., Richmond, Virginia, USA. ACTRASOL products are suppliedby Afton Chemical Corp., Richmond, Virginia, USA. TOMADOL products aresupplied by Air Products, Inc., Allentown, Pennsylvania, USA. BIOSOFTproducts are supplied by Stepan Co., Northfield, Illinois, USA. STEPANOLproducts are supplied by Stepan Co., Northfield, Illinois, USA.ALCOSPERSE products are supplied by AkzoNobel Surface Chemistry LLC,Chicago, Illinois, USA.

Example 5 Gilsonite Dissolution

Three gilsonite-containing compositions were prepared to test thedissolution of the solvent for gilsonite. Gilsonite is a naturallyoccurring form of bitumen. Dissolution of gilsonite correlates well withasphaltene dissolution. Sample 3A contained 0.1 g. of gilsonite and 4.9g. of toluene. Sample 3B contained 0.1 g. of gilsonite and 4.9 g. of thefollowing solution: 85 wt % methyl 9-dodecenoic acid, 5 wt %cyclohexanone, 3 wt % oleic acid, and 7 wt % TOMADOL 25-9. Sample 3Ccontained 0.1 g. of gilsonite and 4.9 g. of methyl 9-dodecenoate. Eachof the three compositions was stirred for 24 hours at 300 rpm at roomtemperature. Then three drops of each composition were placed onto whitefilter paper. FIG. 2 shows the spreading of the composition on thefilter paper, with Composition 3A on the far left, Composition 3B in themiddle, and Composition 3C on the far right. The broader spreadingindicated greater dissolution of the gilsonite by the solvent.

Example 6 Rheological Improvement

Rheological studies were conducted to test wax dissolution in oil. Theoil used in an SAE30 oil (Valvoline) and the wax used was wax NAFOL 20A.The tests were conducted on five samples: Composition 3A: 5 wt % wax inoil; Composition 3B: 5 wt % wax in oil doped with 600 ppm Composition 1Band 300 ppm BASOFLUX RD4120; Composition 3C: 5 wt % wax in oil dopedwith 600 ppm Composition 1B; Composition 3D: 5 wt % wax doped with 300ppm BASOFLUX RD4120; and Composition 3E: oil.

The five samples, viscosity was measured as a function of temperature ata constant shear rate of 10 s⁻¹. Each sample was heated to about 45° C.above the wax appearance temperature and then cooled at a constant rateof 2° C./minute. FIG. 3 shows the rheogram of the results. The verticalaxis is viscosity, measured in Pa·s, and the horizontal axis istemperature measured in ° C. The curve for Composition 3A is labeled asA, the curve for Composition 3B is labeled as B, the curve forComposition 3C is labeled as C, the curve for Composition 3D is labeledas D, and the curve for Composition 3E is labeled as E. Note that thelabels for each curve appear immediately above the respective curve. Thecurve for Composition 3B is labeled twice to show its continuity as itcrosses over the curve for Composition 3A.

1. A composition for dissolving petroleum wax or asphaltenes, thecomposition comprising olefinic ester compounds, wherein the olefinicester compounds are C₁₋₆ alkanol esters of C₁₀₋₁₈ carboxylic acidshaving one or more carbon-carbon double bonds.
 2. The composition ofclaim 1, wherein the olefinic ester compounds make up at least 50percent by weight, or at least 60 percent by weight, or at least 70percent by weight, or at least 80 percent by weight, or at least 90percent by weight, or at least 95 percent by weight of the composition,based on the total weight of the composition. 3-5. (canceled)
 6. Thecomposition of claim 2, further comprising a surfactant.
 7. (canceled)8. (canceled)
 9. The composition of claim 6, wherein the surfactant is anon-ionic surfactant.
 10. The composition of claim 9, wherein thenon-ionic surfactant comprises one or more alkoxylated fatty acids, suchas non-ionic surfactants having a hydrophilic-lipophilic balance (HLB)ranging from 4 to 10, or from 5 to 9, or from 6 to 8, where HLB isdetermined by Griffin's Method.
 11. The composition of claim 9, whereinthe surfactant has a molecular weight ranging from 200 amu to 800 amu,or from 250 amu to 700 amu, or from 300 amu to 600 amu. 12-15.(canceled)
 16. The composition of claim 1, wherein the composition issubstantially free of water. 17-20. (canceled)
 21. The composition ofclaim 1, wherein at least 50 percent by weight, or at least 60 percentby weight, or at least 70 percent by weight, or at least 80 percent byweight of the olefinic ester compounds in the composition are methylesters of C₁₀₋₁₂ carboxylic acids having one carbon-carbon double bond.22. The composition of claim 21, wherein at least 50 percent by weight,or at least 60 percent by weight, or at least 70 percent by weight, orat least 80 percent by weight of the olefinic ester compounds in thecomposition are methyl esters of 9-decenoic acid, 9-undecenoid acid, or9-dodecenoic acid.
 23. The composition of claim 22, wherein at least 50percent by weight, or at least 60 percent by weight, or at least 70percent by weight, or at least 80 percent by weight of the olefinicester compounds in the composition are methyl 9-dodecenoate. 24.(canceled)
 25. (canceled)
 26. The composition of claim 1, wherein theolefinic ester compounds are compounds of formula (I):

wherein: R¹ is C₉₋₁₇ alkenyl; and R² is C₁₋₆ alkyl.
 27. The compositionof claim 26, wherein R¹ is C₉₋₁₁ alkenyl. 28-30. (canceled)
 31. Thecomposition of claim 26, wherein R¹ is —(CH₂)₇—CH═CH—CH₂—CH₃. 32.(canceled)
 33. (canceled)
 34. The composition of claim 26, wherein R² ismethyl. 35-37. (canceled)
 38. The composition of claim 1, wherein thecomposition is a cleaning composition, useful for cleaning petroleum waxor asphaltene deposits.
 39. The composition of claim 1, wherein thecomposition is a petroleum additive composition.
 40. A petroleumcomposition comprising: a petroleum fluid; and a petroleum additivecomposition of claim
 39. 41-51. (canceled)
 52. A method of reducingagglomerates in a petroleum fluid, comprising: providing a petroleumfluid comprising one or more agglomerating materials, the agglomeratingmaterials comprising asphaltenes, petroleum waxes, or a combinationthereof; and introducing to the petroleum fluid the petroleum additivecomposition of claim 39 to form a treated petroleum fluid.
 53. Themethod of claim 52, wherein the introducing comprises adding thepetroleum additive composition to the petroleum fluid in an amount suchthat the petroleum additive composition makes up no more than 5 percentby weight, or no more than 3 percent by weight, or no more than 2percent by weight, or no more than 1 percent by weight, of the treatedpetroleum composition, based on the total weight of the treatedpetroleum composition. 54-56. (canceled)
 57. The method of claim 52,wherein the one or more agglomerating materials comprisemacrocrystalline waxes, microcrystalline waxes, or combinations thereof.58-63. (canceled)